CN115521500A - Preparation method of ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene - Google Patents

Preparation method of ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene Download PDF

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CN115521500A
CN115521500A CN202211187139.2A CN202211187139A CN115521500A CN 115521500 A CN115521500 A CN 115521500A CN 202211187139 A CN202211187139 A CN 202211187139A CN 115521500 A CN115521500 A CN 115521500A
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resin solution
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CN115521500B (en
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魏子栋
王建川
袁伟
张涛昌
王鑫陈
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Chongqing University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract

The invention provides an ultrathin high-strength composite proton exchange membrane based on biaxially stretched porous ultrahigh molecular weight polyethylene and a preparation method thereof, wherein perfluorinated sulfonic acid resin is compounded with a porous ultrahigh molecular weight polyethylene film with ultrathin thickness and high strength, and proper surface treatment is added, so that the two materials are well compatible, and a composite membrane prepared in a large scale through a casting machine has the advantages of compact structure, ultrathin thickness of 4 mu m, high mechanical strength of 115MPa, extremely low water absorption swelling, gas permeation and high conductivity, so that the generation of defective pore channels of the composite membrane is avoided, the fuel crossing is effectively prevented, and excellent fuel cell performance is shown.

Description

Preparation method of ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene
1. The technical field is as follows:
the invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of an ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene.
2. Background art:
the hydrogen fuel cell has the outstanding advantages of extremely high energy conversion efficiency, extremely high energy density and zero pollution, and is one of key technologies for solving the global warming problem and realizing the aim of 'double carbon'. Among them, proton exchange membrane fuel cells are most widely used in the field of electric vehicles. The proton exchange membrane is a key component thereof, relating to fuel cell power output, life and cost. Therefore, the ideal proton exchange membrane needs to have the advantages of higher proton conductivity, low gas permeability, high mechanical properties, excellent chemical stability and low cost.
At present, the proton exchange membrane with the best application prospect at home and abroad mostly adopts a porous basement membrane composite reinforcement strategy, and the proton exchange membrane tends to be thinner. However, the composite reinforced film has the compatibility problem of perfluorinated sulfonic acid resin and a substrate film, and the conductivity and the gas permeability of the film are influenced; the most used porous PTFE base membrane has low mechanical property, and the prepared composite membrane has general mechanical property (less than 30 MPa); in addition, the PTFE porous membrane has higher cost, and the prepared composite membrane has difficult advantage in cost. Therefore, the development of a porous composite proton exchange membrane with good compatibility, ultrathin thickness, high mechanical property and low cost is an important link for the future development of fuel cells.
3. The invention content is as follows:
the invention aims to solve the problems of thickness, mechanical property, compatibility with a porous base membrane, cost and the like of a proton exchange membrane, and provides an ultrathin high-strength composite proton exchange membrane based on biaxially-stretched porous ultrahigh molecular weight polyethylene and a preparation method thereof.
The invention provides a preparation method of an ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene, which comprises the following steps:
(1) Surface treatment: treating the surface of the biaxially stretched ultrahigh molecular weight polyethylene porous film to obtain an activated base film;
(2) Preparing a perfluorosulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at 50-100 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 10-50 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 0.5 to 5 hours to remove air bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) putting the impregnated membrane into a normal-pressure oven through a scraper with the height range of 100-500 mu m, and drying at the temperature of 60-100 ℃ for 1-5h to obtain the ultrathin high-strength composite proton exchange membrane with the thickness of 3-20 mu m and based on the biaxially stretched ultrahigh molecular weight polyethylene.
Optionally, the biaxially stretched ultrahigh molecular weight polyethylene porous film in step (1) has the characteristics that: biaxial stretching, nano fiber net shape, thickness of 3-10 μm, pore diameter of 50-500nm, porosity of 50-80%, mechanical strength of 200-400MPa, elongation at break of 20-80%, and crystallinity of 30-70%.
Optionally, the surface treatment method in step (1) includes ultraviolet radiation treatment, plasma treatment, active solvent treatment and surface oxidation treatment; wherein, the ultraviolet radiation treatment is carried out, and the wavelength range is 50-300nm; the plasma treatment is carried out at a pressure of 5-10KPa and with a plasma gas of N 2 、O 2 、NH 3 、CO 2 Ar, he and H 2 One of O; treating the active solvent, wherein the solvent is one or more of methanol, ethanol, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; and in the surface oxidation treatment, the solvent in the oxidation solution is water, and the solute is one or more of potassium dichromate, potassium permanganate, nitric acid, nitrous acid, hypochlorous acid and hydrogen peroxide.
Optionally, the polar solvent in step (2) is one or more of tetrahydrofuran, acetonitrile, methanol, ethanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
After the technical scheme is adopted, the invention mainly has the following advantages:
(1) The ultrahigh molecular weight polyethylene material and the perfluorinated sulfonic acid resin have better compatibility, and proper surface treatment is added to enhance the hydrophilicity of the base membrane, so that the prepared composite proton exchange membrane forms a compact internal structure, and fuel crossing can be effectively prevented;
(2) The ultra-high molecular weight polyethylene porous film has the characteristics of biaxial stretching and moderate crystallization, so that the ultra-high molecular weight polyethylene porous film has high strength and ultra-thin thickness, and the prepared composite film well inherits the two points, so that the thickness can reach ultra-thin 4 mu m at the lowest, and the mechanical strength also reaches over 150 MPa;
(3) The cost price of the ultra-high molecular weight polyethylene porous film is far lower than that of the PTFE film, so that the prepared composite film has more advantages in cost;
(4) The prepared composite proton exchange membrane shows excellent performance in fuel cell application.
4. Description of the drawings:
FIG. 1 is a Scanning Electron Microscope (SEM) image of an ultra-thin high-strength composite proton exchange membrane based on biaxially stretched ultra-high molecular weight polyethylene, the left image is a plane, and the right image is a cross section;
FIG. 2 is a graph of the mechanical properties of the prepared composite membrane and Nafion HP membrane;
fig. 3 is a graph of fuel cell performance of the composite membrane prepared.
5. The specific implementation mode is as follows:
the invention will be further described with reference to the following specific embodiments:
example 1
A preparation method of an ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene comprises the following steps:
(1) Surface treatment: treating the surface of the biaxially stretched ultrahigh molecular weight polyethylene porous film to obtain an activated base film;
(2) Preparing a perfluorinated sulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at the temperature of 60 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 20 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 1 hour to remove bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; the impregnated membrane enters a normal pressure oven through a scraper with the height range of 100 mu m, and is dried for 2 hours at the temperature of 80 ℃ to obtain the composite proton exchange membrane with the thickness of 4 mu m and based on biaxial stretching ultra-high molecular weight polyethylene ultrathin high strength;
(4) Performance testing of composite proton exchange membranes
And (3) testing the appearance of the composite film: brittle-breaking the composite proton exchange membrane prepared in the step (3) under liquid nitrogen, and observing the surface and section morphology of the composite proton exchange membrane by using an SEM (scanning Electron microscope), wherein the composite proton exchange membrane is shown in figure 1;
and (3) testing the mechanical properties of the composite film: cutting a 1cm multiplied by 4cm composite proton exchange membrane sample prepared in the step (3), placing the sample in pure water for 24 hours, quickly wiping off surface water, and testing the mechanical property of the sample by using a MTS (MTS) tensile tester (E44.104) type universal material testing machine, wherein the testing temperature is 25 ℃, and the stretching speed is 5mm/min, so as to obtain a curve shown in figure 2;
testing water absorption swelling, conductivity and Ion Exchange Capacity (IEC) of the composite membrane: the water absorption swelling test is that the composite membrane is soaked in pure water for 24 hours at the temperature of 25 ℃, and the percentage of the mass and the size change of the composite membrane before and after soaking is measured; the conductivity test is to directly test the composite proton exchange membrane sample prepared in the step (3) of 1cm multiplied by 4cm by using a Solartron1287&1260 alternating current impedance instrument at the temperature of 25 ℃; the IEC test was performed by a common acid-base titration method, and the test results are shown in table 1.
Example 2
A preparation method of an ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene comprises the following steps:
(1) Surface treatment: treating the surface of the biaxially stretched ultrahigh molecular weight polyethylene porous film to obtain an activated base film;
(2) Preparing a perfluorosulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at 80 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 30 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 2 hours to remove bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) feeding the impregnated membrane into a normal-pressure oven through a scraper with the height range of 150 mu m, and drying for 2 hours at the temperature of 70 ℃ to obtain the composite proton exchange membrane with the thickness of 8 mu m and based on biaxial stretching ultra-high molecular weight polyethylene ultrathin high strength.
Example 3
A preparation method of an ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene comprises the following steps:
(1) Surface treatment: treating the surface of the ultrahigh molecular weight polyethylene porous film to obtain an activated substrate film;
(2) Preparing a perfluorinated sulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at 90 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 20 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 3 hours to remove bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) the impregnated membrane enters a normal-pressure oven through a scraper with the height range of 200 mu m, and is dried for 2 hours at the temperature of 90 ℃ to obtain the composite proton exchange membrane with the thickness of 10 mu m and based on biaxial stretching ultra-high molecular weight polyethylene, ultrathin and high strength.
Comparative example
Comparative experimental example a commercial Nafion HP membrane was selected and the test method was the same as example 1 except for the fuel cell test.
Test results of the present invention:
the performance test results of the composite proton exchange membrane prepared in example 1 and the proton exchange membrane prepared in comparative example are shown in the following table 1:
thickness/mum IEC/mmol g -1 Swelling ratio/% Conductivity mS cm -1 Tensile strength/MPa
Comparative example 20 1.1 5.0 74 33
Example 1 4 0.8 2.4 150 115
As can be seen from Table 1, the ultra-thin high-strength composite proton exchange membrane based on biaxially stretched ultra-high molecular weight polyethylene prepared by the invention has lower thickness, lower water absorption and swelling, higher electrical conductivity and higher mechanical strength compared with a commercial Nafion HP membrane, and the composite membrane has better application prospect. In addition, SEM images show that the biaxially stretched ultrahigh molecular weight polyethylene and the perfluorosulfonic acid resin have a good compact interface, good compatibility of two materials is realized, the generation of a defective pore passage of a composite membrane is avoided, and fuel crossing is effectively prevented, so that the peak power density of a fuel cell can be as high as 1.4W cm in a single cell test -2 。

Claims (7)

1. A preparation method of an ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene comprises the following steps:
(1) Surface treatment: treating the surface of the biaxially stretched ultrahigh molecular weight polyethylene porous film to obtain an activated base film;
(2) Preparing a perfluorinated sulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at 50-100 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 10-50 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 0.5 to 5 hours to remove air bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) putting the impregnated membrane into a normal-pressure oven through a scraper with the height range of 100-500 mu m, and drying at the temperature of 60-100 ℃ for 1-5h to obtain the ultrathin high-strength composite proton exchange membrane with the thickness of 3-20 mu m and based on the biaxially stretched ultrahigh molecular weight polyethylene.
2. The method for preparing the ultrathin high-strength composite proton exchange membrane based on the biaxially stretched ultrahigh molecular weight polyethylene according to claim 1, wherein the biaxially stretched ultrahigh molecular weight polyethylene porous membrane in the step (1) is characterized in that: biaxial stretching, nano fiber net shape, thickness of 3-10 μm, pore diameter of 50-500nm, porosity of 50-80%, mechanical strength of 200-400MPa, elongation at break of 20-80%, and crystallinity of 30-70%.
3. The method for preparing the ultra-thin high-strength composite proton exchange membrane based on the biaxially stretched ultra-high molecular weight polyethylene according to claim 1, wherein the surface treatment method in the step (1) comprises ultraviolet radiation treatment, plasma treatment, active solvent treatment and surface oxidation treatment; wherein, the ultraviolet radiation treatment is carried out, and the wavelength range is 50-300nm; the plasma treatment is carried out at a pressure of 5-10KPa and with a plasma gas of N 2 、O 2 、NH 3 、CO 2 Ar, he and H 2 One of O; treating the active solvent, wherein the solvent is one or more of methanol, ethanol, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; and in the surface oxidation treatment, the solvent in the oxidation solution is water, and the solute is one or more of potassium dichromate, potassium permanganate, nitric acid, nitrous acid, hypochlorous acid and hydrogen peroxide.
4. The method for preparing the ultra-thin high-strength composite proton exchange membrane based on the biaxially stretched ultra-high molecular weight polyethylene according to claim 1, wherein the polar solvent in the step (2) is one or more of tetrahydrofuran, acetonitrile, methanol, ethanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
5. The preparation method of the ultrathin high-strength composite proton exchange membrane based on the biaxially stretched ultrahigh molecular weight polyethylene according to claim 1, characterized in that the steps (1), (2) and (3):
(1) Surface treatment: treating the surface of the biaxially stretched ultrahigh molecular weight polyethylene porous film to obtain an activated base film;
(2) Preparing a perfluorinated sulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at the temperature of 60 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 20 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 1h to remove air bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) feeding the impregnated membrane into a normal-pressure oven through a scraper with the height range of 100 mu m, and drying for 2 hours at the temperature of 80 ℃ to obtain the biaxial-tension ultra-high molecular weight polyethylene-based ultrathin high-strength composite proton exchange membrane with the thickness of 4 mu m.
6. The preparation method of the ultrathin high-strength composite proton exchange membrane based on the biaxially stretched ultrahigh molecular weight polyethylene according to claim 1, characterized in that the steps (1), (2) and (3):
(1) Surface treatment: treating the surface of the biaxially stretched ultrahigh molecular weight polyethylene porous film to obtain an activated base film;
(2) Preparing a perfluorosulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at 80 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 30 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 2 hours to remove bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) feeding the impregnated membrane into a normal-pressure oven through a scraper with the height range of 150 mu m, and drying for 2 hours at the temperature of 70 ℃ to obtain the composite proton exchange membrane with the thickness of 8 mu m and based on biaxial stretching ultra-high molecular weight polyethylene ultrathin high strength.
7. The method for preparing the ultrathin high-strength composite proton exchange membrane based on the biaxially stretched ultrahigh molecular weight polyethylene according to claim 1, wherein the steps (1), (2) and (3):
(1) Surface treatment: treating the surface of the ultra-high molecular weight polyethylene porous film to obtain an activated substrate film;
(2) Preparing a perfluorinated sulfonic acid resin solution: firstly, dissolving perfluorosulfonic acid resin in a polar solution, stirring the solution at 90 ℃ until the perfluorosulfonic acid resin is completely dissolved, and preparing a resin solution with the mass concentration of 20 wt%; secondly, placing the resin solution in a vacuum defoaming machine for 3 hours to remove air bubbles in the resin solution;
(3) Tape casting: pouring a resin solution into a solution tank of a casting machine, and enabling the biaxially stretched ultrahigh molecular weight polyethylene porous film subjected to surface treatment to pass through the solution tank to obtain an impregnated film of the base film impregnated with the resin solution; and (3) the impregnated membrane enters a normal-pressure oven through a scraper with the height range of 200 mu m, and is dried for 2 hours at the temperature of 90 ℃ to obtain the composite proton exchange membrane with the thickness of 10 mu m and based on biaxial stretching ultra-high molecular weight polyethylene, ultrathin and high strength.
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CN109997247A (en) * 2016-11-17 2019-07-09 香港科技大学 Nanoporous ultra-high molecular weight polyethylene film
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